2,4&#39;dioxo-1,3-benzoxazinothionophosphonic acid esters

ABSTRACT

2,4-Dioxo-1,3-benzoxazinothionophosphonic acid esters which possess arthropodicidal, especially insecticidal or acaricidal, properties. The compounds have the structure   IN WHICH R and R1 stand for the same or different straight-chain or branched lower alkyl radicals.

ilnited States Patent Lorenz et al.

2,4DIOXO-l,3- BENZOXAZINOTHIONOPHOSPHONIC ACID ESTERS Inventors: WalterLorenz, Wuppertal-Cronenberg; lngeberg Hammann, Cologne, both of GermanyFarbeniabriken Bayer Aktiengesellschaft, Leverkusen, Germany Filed:Sept. 23, 1970 Appl. No.: 74,856

Assignee:

Foreign Application Priority Data Oct. 7, 1969 Germany ..P 19 50 492.8

US. Cl. ..260/244 R, 424/248 Int. Cl. ..C07d 87/08 Field of Search..260/244 References Cited UNITED STATES PATENTS 9/ 1969 Nakanishi260/244 R [451 Feb. 20, 1973 2,706,l94 4/1955 Morris et al. ..260/244Primary Examiner-Harry l. Moatz Attorney-Burgess, Dinklage & Sprung [57]ABSTRACT in which R and R stand for the same or different straight-chainor branched lower alkyl radicals.

5 Claims, No Drawings R and R stand for the same or differentstraightchain or branched lower alkyl radicals.

These compounds have been found to have strong insecticidal andacaricidal properties.

The invention also provides a process for the production of a2,4-dioxo-1,3-benzoxazinothionophosphonic acid ester of the formula (I)in which 3-hydroxy-2,4- dioxo-l ,3-benzoxazine of the formula isreacted, either in the form of its alkali metal, alkaline earth metal orammonium salt or in the presence of an acid-binding agent, with anO-alkyl alkanethionophosphonic acid ester halide of the formula S ORHalP

1 (III) in which R and R have the meaning stated above, and

Hal stands for a halogen atom.

Surprisingly, the 2 ,4-dioxol ,3-benzoxazinothionophosphonic acid esters(l) are distinguished by a considerably better insecticidal andacaricidal activity than the known 2,4-dioxo-l,3-benzoxazinothionophosphoric acid esters of analogous constitution andthe same type of activity. The substances according to the inventiontherefore represent a genuine enrichment of the art.

If, for example, 3-hydroxy-2,4-dioxo-l,3-benzoxazine andO-rnethyl-methanethionophosphonic acid ester chloride are used asstarting materials, the reaction course can be represented by thefollowing formula scheme:

Preferably, R and R stand for alkyl radicals with one to four andespecially one or two carbon atoms, and Hal stands for a chlorine atom.

As examples of thionophosphonic acid ester halides which can be used inthe present process, there may be mentioned: O-methyl-methane,O-ethyl-methane, O- ethyl-ethane, O-methyl-ethane, O-isopropyl-methane,O-isopropyl-isopropane, O-methyl-isopropane, and O-ethyl-isopropane-thionophosphonic acid ester chloride.

The thionophosphonic acid ester halides (Ill) and 3-hydroxy-2,4-dioxobenzoxazine to be used as starting materials aredescribed in the literature and can be prepared according to knownmethods.

The reaction of the invention may be carried out in the presence of asolvent which term includes a mere diluent. All organic solvents ordiluents are suitable. These include aliphatic and aromatichydrocarbons, which may be chlorinated, such as benzene, toluene,xylene, benzine, methyl chloride, chloroform, carbon tetrachloride,chlorobenzene; ethers, such as diethyl ether, dibutyl ether, dioxane;ketones, such as acetone, methylethyl ketone, methylisopropyl ketone,methylisobutyl ketone', nitriles, such as acetonitrile; and the like.

As acid acceptors, all customary acid-binding agents are suitable.Particularly suitable have proved to be alkali metal carbonates andalcoholates, for example sodium or potassium carbonate, methylate orethylate; and aliphatic, aromatic or heterocyclic amines, for exampletriethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine orpyridine.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the reaction is carried out at from about 10 to +60 C,preferably at 0 to 30 C.

Usually, the reaction proceeds at normal pressure.

In carrying out of the process, the starting materials may generally beused in equimolar proportion. An excess of one or other of the reactantsbrings no substantial advantages.

The reaction may be carried out in a suitable solvent in the presence ofan acid acceptor, and the reaction mixture may be stirred afterwards forsome hours. The mixture may be subsequently poured into acidified waterand.worked up as usual.

The compounds according to the invention are obtained in most cases incrystalline form; they may be characterized by their elemental analysesand their melting points.

As already mentioned above, the products according to the invention aredistinguished by an outstanding insecticidal and acaricidal activity,with only slight phytotoxicity. The pesticidal effect sets in rapidlyand is long-lasting. By reason of these properties, the new substancesare used in crop protection and the protection of stored products, aswell as in the hygiene field, for the control of noxious sucking andbiting insects, as well as of mites.

To the sucking insects there belong, in the main, aphids (Aphidae) suchas the green peach aphid (Myzus persicae), the bean aphid (Doralisfabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid(Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), thecurrant gall aphid (Cryptomyzus korschelti), the mealy apple aphid(Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and thecherry black-fly (Myzus cerasi); in addition, scales and mealybugs(Coccina), for example the oleander scale (Aspidiotus hederae) and thesoft scale (Lecam'um hesperidum) as well as the grape mealybug(Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinothripsfemoralis, and bugs, for example the beet bug (Piesma quadrata), thecotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), theassassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans)and, further, cicadas, such as Euscelis bilobatus and Nephotcttixbipunctatus; and the like.

In the case of the biting insects, above all there should be mentionedbutterfly caterpillars (Lepidopitem) such as the diamond-back moth(Plutella maculipennis), the gypsy moth (Lymantria dispar), the

brown-tail moth (Euproctis chrysorrhoea) and tent caterpillar(Malacosoma neustria); further, the cabbage moth (Mainestra brassicae)and the cutworm (Agrotis segetum), the large white butterfly (Pierisbrassicae), the small winter moth (Cheimatobia brumata), the green oaktortrix moth (Tortrix viridana), the fall armyworm (Laphygma frugiperda)and cotton worm (Prodenia litura), the ermine moth (Hyponomeutapadella), the Mediterranean flour moth (Ephestia kuhniella) and greaterwax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects are beetles (Coleoptera), forexample the granary weevil (Sitophilus granarius Calandra granaria), theColorado beetle (Leptinotarsa decemlineara), the dock beetle(Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), theblossom beetle (Meligethes census), the raspberry beetle (Byturustomentosus) the bean weevil (Bruchidius Acamhoscelides obtectus), theleather beetle (Dermestes frischi), the khapra beetle (T rogodermagranarium), the flour beetle (Tribolium castaneum), the northern cornbillbug (Calandra or Sitophilus zeamais), the drugstore beetle(Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and thesaw-toothed grain beetle (Oryzaephilus surinamensis) and also speciesliving in the soil, for example wireworms (Agriotes spec.) and larvae ofthe cockchafer (Melolantha melolontha); cockroaches, such as the Germancockroach (Blattella germanica), American cockroach (Periplanetaamericana), Madeira cockroach (Leucophaea or Rhyparobia madeirae),Oriental cockroach (Blatra orientalis), the giant cockroach (Blaberusgiganteus) and the black giant cockroach (Blaberus fuscus) as well asHenschoutedenia flexivitta; further, Orthoptera, for example the housecricket (Acheta domesticus); termites such as the eastern subterraneantermite Reticulitermes flavipes) and Hymenoptera such as ants, forexample the garden ant (Lasius niger); and the like.

The Diptera comprise essentially the flies, such as vinegar fly(Drosophila melanogaster), the Mediterranean fruit fly (Ceratitiscapirata), the house fly (Musca domestica), the little house fly (Fanniacam'cu- Ian's), the black blow fly (Phormia aegina) and bluebottle fly(Calliphora erythrocephala) as well asthe stable fly (Stomoxyscalcitrans); further, gnats, for example, mosquitoes such as the yellowfever mosquito (Aedes aegypti), the northern house mosquito (Culexpipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acari) there are classed, in particular, the spidermites (Tetranychidae) such as the twospotted spider mite (Tetranychustelarius Tetranychus althaeae or Tetranychus urticae) and the Europeanred mite (Paratetranychus pilosus Panonychus ulmi), blister mites, forexample the currant blister mite (Eriophyes ribis) and tarsonemids, forexample the broad mite (Hemimrsonemus latus) and the cyclamen mite(Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick(Ornithodorus m0ubata);and the like.

When applied against hygiene pests and pests of stored products,particularly flies and mosquitoes, the new compounds are alsodistinguished by an outstanding residual activity on wood and clay aswell as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents or extenders of the typeusable in conventional pesticide formulations or compositions, e.g.conventional pesticide dispersible carrier vehicles such as solutions,emulsions, suspensions, emulsifrable concentrates, spray powders,dusting agents, granules, etc. These are prepared in known manner, forinstance by extending the active compounds with conventional pesticidedispersible liquid diluent carriers and/or dispersible solid carriersoptionally with the use of carrier vehicle assistants, e.g. conventionalpesticide surface-active agents, including emulsifying agents and/ordispersing agents, whereby, for example, in the case where water is usedas diluent, organic solvents may be added as auxiliary solvents. Thefollowing may be chiefly considered for use as conventional carriervehicles for this purpose: inert dispersible liquid diluent carriers,including inert organic solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, etc.), halogenated, especially chlorinated,aromatic hydrocarbons (e.g. chlorobenzenes, etc), paraffins (e.g.petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylenechloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol,etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols, (e.g.glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.),sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.)and/or water; as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g. kaolins, alumina,silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) andground synthetic minerals (e.g. highly dispersed silicic the form ofmixtures with one another and/or with such solid and/or liquiddispersible carrier vehicles and/or with other known compatible activeagents, especially plant protection agents, such as other acaricides andinsecticides, or rodenticides, fungicides, herbicides, bactericides,etc., if desired, or in the form of particular dosage preparations forspecific application made therefrom, such as solutions, emulsions,suspensions,

powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95 percent byweight, and preferably 05-90 percent by weight, of the mixture, whereascarrier composition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0005-20 percent,preferably 0.005-5 percent, by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as (l) a dispersibleinert finely divided carrier solid, and/or (2) a dispersible carrierliquid such as an inert organic solvent and/or water preferablyincluding a surface-active effective amount of a carrier vehicleassistant, e.g. a surface-active agent, such as an emulsifying agentand/or a dispersing agent, and an amount of the active compound which iseffective for the purpose in question and which is generally betweenabout 0.0005-95 percent, and preferably 0.005-95 percent, by weight ofthe mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. in this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95 percent by weight ofactive compound or even the 100 percent active substance alone, e.g.about 20-100 percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. arthropods, i.e. insectsand acarids, and more particularly methods of combating at least one ofinsects and acarids which comprises applying to at least one ofcorrespondingly (a) such insects, (b) such acarids, and (c) thecorresponding habitat thereof, i.e. the locus to be protected, acorrespondingly combative or toxic amount, i.e. an arthropodicidally,especially insecticidally or acaricidally, effective amount of theparticular active compound of the invention alone or together with acarrier vehicle as noted above. The instant formulations or compositionsare applied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

EXAMPLE I Plutella test Solvent: 3 parts by weight acetone Emulsifier: 1part by weight alkylaryl polyglycol ether To produce a suitablepreparation of active compound, 1 part by weight of the active compoundis mixed with the stated amount of solvent containing the stated amountof emulsifier and the concentrate is diluted with water to the desiredconcentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dew moist and are then infested withcaterpillars of the diamondback moth (Plutella maculipennis).

After the specified periods of time, the degree of destruction isdetermined as a percentage: percent means that all the caterpillars arekilled whereas 0 per cent means that none of the caterpillars arekilled.

The active compounds, the concentrations of the active compounds, theevaluation times and the results c an be seen gorrrlable l. 7

TABLE 1 (Plutella test) Concentration Degree of of active destructioncompound in percent Active compound (constitution) in percent after 3days (A) O 0. l 0

S u u (CHJOJ P-O-N (known).

(1),, 0 0.1 100 ll 0. ()l 100 C 0. 001 100 I) O N l]. 0001 (i5 CH O O iO -N 1 (lnlIsO I Solvent: 3 parts by weight acetone Emulsifier: 1 partby weight alkylaryl polyglycol ether To produce a suitable preparationof active compound, 1 part by weight of the active compound is mixedwith the stated amount of solvent containing the stated amount ofemulsifier, and the concentrate is diluted with water to the desiredconcentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dripping wet and then infested with mustardbeetle larvae (Phaedon cochleariae).

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100 percent means that all the beetle larvaeare killed. percent means that none of the beetle larvae are killed.

The active compounds, the concentration of the active compound, thetimes of evaluation and the results can be seen from the following Table2.

TABLE 2 (llmodou lurvim test) (loucvntmtlon Dvm'vo of of activedestruction compound in pvrcnnl. Aotlvn compound (uonstltutlou) inpercent llll-l'l' ll (lllyS (A), 0 0. l o

S H (CHaO) P-0-N (known).

(1) (H) 0. 1 100 0.01 100 CH3 S CHSO (2) (a 0. 1 100 CH3 S 0.01 1000.001 90 /PON CzHsO 0 (3) (I? [Li 100 C2H5 S 100 0.001 50 /PON 091150OLI EXAMPLE 3 Myzus test (contact action) Solvent: 3 parts by weightacetone Emulsifier: 1 part by weight alkylaryl polyglycol ether Toproduce a suitable preparation of active compound, 1 part by weight ofthe active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier and the concentrate isdiluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested withpeach aphids (Myzus persicae) are sprayed with the preparation of theactive compound until dripping wet.

After the specified periods of time, the degree of destruction isdetermined as a percentage: percent means that all the aphids are killedwhereas 0 percent means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 3.

TABLE 3 (Myzus test) Couocntrn- Degree of tion of octivo destructionActlvo compound compound in port-nut (constitution) in port-out nftor 24hours (A)... 0. l l) H u (CH O);P()N i l O 0 (known).

l (Czlls ))zl-Q "N I (known). (0....

. 0.] Ion ""Ki 0. 01 no It (llI O (2).-.- J 0.1 as CH3 S 0.01 U8 \ll/PON 0211 0 0 i ZHsO The following further examples are set forth toillustrate, without limitation, the process for producing the activecompounds according to the present invention.

EXAMPLE 4 o A 5 ca.

ocul (l 99 g (0.55 mole) of 3-hydroxy-l,3 -benzoaxazine-2,4 -dione(prepared according to U.S. Pat. No. 2,714,105; m.p. 235236 C) aredissolved in 200 ml of pyridine. To this solution there are addeddropwise, while cooling with ice water, 73 g (0.5 mole) ofO-methylmethanethionophosphonic acid ester chloride, at such a speedthat an internal temperature of 30 C is not exceeded, and the mixture,after 1 hours stirring, is poured into water acidified with hydrochloricacid. The initially separating oil very soon solidifies in crystallineform. The crystals are filtered off with suction and washed acid-free.The crude yield of O-methyl-O-[2,4- dioxo-l ,3-benzoxazino-( 3 )-y1]-methanethionophosphonic acid ester is 80 g (55 percent of the theory).By recrystallization from ethanol (1 g/5 ml), the product is obtained inthe form of colorless crystals of m.p. 141 C.

To a solution of 106 g (0.6 mole) of 3-hydroxy-l,3-benzoxazine-2,4-dione (m.p. 235235 C) in 200 ml of pyridine there areadded dropwise at a temperature not exceeding 30 C, with ice cooling, 95g (0.6 mole) of O- ethyl-methanethionophosphonic acid ester chloride,and the mixture, after 1 hours stirring, is poured into water acidifiedwith hydrochloric acid. The product separating in oily form soonsolidifies in crystalline form. The crystals are filtered off withsuction and washed neutral. The crude yield of O-ethyl-O-[2,4- dioxo- 1,3-benzoxazino-( 3 )-yl]- methanethionophosphonic acid ester is 155 g(86 percent of the theory). From ethanol (1 g/3 ml), colorless crystalsof m.p. 1 11 C are obtained.

N P S Calc. for C H NOJS (molecular weight 301.3): 4.64%; 10.64%;10.28%; Found: 4.70%; 10.81%; 10.47%.

EXAMPLE 6 1n manner analogous with that described above, the compound ofthe following formula is obtained:

s 02H. 11 P N P S Calc. for C l-l NO -,PS (molecular weight 315.3):4.44%; 10.17%; 9.82%; Found: 4.59%; 10.25%; 10.17%.

It will be realized that all of the foregoing compounds contemplated bythe present invention possess the desired selective pesticidal,especially arthropodicidal, i.e. insecticidal or acaricidal, propertiesfor combating insects and acarids, and that such compounds have a lowphytotoxicity and a correspondingly low .mammalian toxicity.

As may be used herein, the terms arthropod," arthropodicidal and"arthropodicide" contemplate specifically both insects and acarids.Thus, the insects and acarids may be considered herein collectively asarthropods to be combated in accordance with the invention, andaccordingly the insecticidal and/or acaricidal activity may be termedarthropodicidal activity, and the concomitant combative or effectiveamount used will be an arthropodicidally effective amount which ineffect means an insecticidally or acaricidally effective amount of theactive compound for the desired purposes.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

l. A 2,4-dioxo-l,3-benzoxazinothionophosphonic acid ester of the formulain which R and R, stand for the same or different straightchain orbranched lower alkyl radicals.

2. A compound according to claim 1 in which R and R stand for methyl orethyl.

3. A compound according to claim 1, wherein such compound isO-methyl-O-[2,4-dioxo-l,3-benzoxazino- (3)-yl]-methanethionophosphonicacid ester of the formula 4. A compound according to claim 1, whereinsuch compound is O-ethyl-O-[2,4-dioxo-l,3-benzoxazino- (3)-yl]-methanethionophosphonic acid ester of the formula 5. A compoundaccording to claim 1, wherein such compound isO-ethyl-O-[2,4-dioxo-1,3-benzoxazino- (3)-yl]-ethanethi0nophosphonicacid ester of the formuia

1. A 2,4-dioxo-1,3-benzoxazinothionophosphonic acid ester of the formula2. A compound according to claim 1 in which R and R1 stand for methyl orethyl.
 3. A compound according to claim 1, wherein such compound isO-methyl-O-(2,4-dioxo-1,3-benzoxazino-(3)-yl)-methanethionophosphonicacid ester of the formula
 4. A compound according to claim 1, whereinsuch compound isO-ethyl-O-(2,4-dioxo-1,3-benzoxazino-(3)-yl)-methanethionophosphonicacid ester of the formula